Separation and purification of gaseous mixtures



May 4, 1943. A. R. POWELL SEPARATION AND PURIFICATION oF GAsEoUs MIXTURES Filed Jan. 15. 1941 INV ENTOR .41. FRE@ 4Q. Powsu.

Patented May 4, 1943 SEPARATION AND PURIFICATION CF GASEOUS MIXTURES Alired R. Powell, Pittsburgh, Pa., assgnor to Koppers Company, a corporation of Delaware Application January 15, 1941, serial No. 374,430

claims. (ol. :a3-3) The present invention relates to an improved cyclic process for continuously removing -hydrogen sulphide from gaseous mixtures also containing variable and relatively large quantities of carbon dioxide.

In Jacobson U. S. Patent 1,390,037, that issued September 6, 1921, to Vthe Koppers Company,

there is set forth a method for purifying gases" of hydrogen sulphide by recycling an alkali-metal carbonate solution in series respectively through absorption and actication steps. This method is principally directed towards the purification of fuel gases, such as coke-oven gas. These gases normally have low carbon dioxide contents of about 1 per cent to 2.5 per cent. In the actication step, spent solution from the absorption step is brought into contact with a current of air which-carries out absorbed hydrogen sulphide present in the solution, the same being liberated in consequence of .the reversible reaction, i. e., NaHS-l-NaHCOaNazCOa-l-Hzs, the current of air serving to displace the reaction to the right and thereby upsetting the equilibrium.

vThe process of said patent which is well known as the so-called Seaboard process is primarily directed to the removal of hydrogen sulphide from gaseous mixtures and substantially only this constituent is removed in the actication step for spent solution. With signicant increase in the carbon dioxide content of the gaseous mixbeing treated there still remains sufficient of the gen sulphide absorption eiliciency of the solution regardless of the carbon 'dioxide content of the to-be-puriiied gases. The present application is a continuation in part of the said Powell application.

An object ofthe present invention is to provide an improved actiflcation step for the Seaboard process in which not only hydrogen sulphide is removed but also more strongly acidic gases, such as carbon dioxide.

A further object of the present invention is to provide means whereby the well-known Seaboard process for extracting hydrogen sulphide from gaseous mixtures becomes of improved utility when employed for gases containing varying quantities of carbon dioxide or such higher contents thereof that-the scrubbing solution would be otherwise rapidly depleted of ,its hydrogen sulphide absorption capacity; l l

A further object of the present invention is to provide means whereby the bulk of the hydrogen sulphide present in spent alkali-metalI carbonate solutions from gas purification processes can be removed by the economical aeration method and the bicarbonate contentthereof be independently-regulated.

A further object is to provide an improved method for actifying spent solution from the Seaboard process whereby the amount of reagent present therein in the form of the carbonate itself can be maintained at an optionally regulacarbonate present in the scrubbing solution to give eicient hydrogen sulphide 'removal in the v absorption step. The Seaboard process has many advantages because of its' simple and economical operation. It is highly desirable that it be adapted for use in purifying gases containing higher ble level. l

A further object of the present invention is to provide means for regulating not only the hydrogen sulphide content but also the carbon dioxide content of the recycled scrubbing solution.

The invention has for further objects such other improvements and vsuch other operative advantages or results as may be found to obtain in the process or apparatus hereinafter described or claimed.

According to the present invention spent solutions from an absorption step for removing both hydrogen sulphide and carbon dioxide from gaseous mixtures are actled in two stages, first in an aeration stage and subsequently by boiling.

As above mentioned, the Seaboard process comprises essentially. an absorption step for the removal of hydrogen sulphide from a mixture 4containing the same followed by an actiiicationA step wherein spent scrubbing solution is aerated by being passed downwardly counter-current to an updraft lof air thereby to remove the absorbed hydrogen sulphide. In the present improvement some of the so-aerated solution is continuously subjected to heating under conditions for removing a regulated amount of carbon dioxide therefrom, that is, preferably that amount of carbon dioxide absorbed in the absorption step and which it is necessary to remove to maintain the scrubbing solution at a preferred absorption elciency. rPhat part of the solutionractiiied only by aeration is preferably returned to the absorption step independently of that portion of the solution actif-led by aeration and heat, the latter being returned to said absorption step at a point therein subsequent to that at which the air-actied solution is introduced. Such point of introduction for'the solution portion actied by aeration and heat is advantageous because with its higher alkali-metal carbonate content it can moreeffectively-remove small traces of hydrogen sulphide in the gas leaving contact with the bulk 'of the solution that has been actied only by aeration.

In the accompanying drawing forming a part of this specification and showing for purposes of exemplication a preferred apparatus and method in which the invention may be embodied andpracticed but without limiting the claimed invention specifically toV such illustrative instance or instances:

The single rlgureis a diagrammatic representation in elevation, with parts broken away,

of apparatus for carrying out the improved gas theqabs'o'rber through line Il.- It is to be under-` stood' that wherevergthe sodium salt is mentioned the potassiumpsaltlis equally effective. In

While various types of gas and liquid con- 2,318,523 flowed to a further treating step wherein it is actifier apparatus 9 is shown with hurdle-construction packing I0.

The spent solution reaching the bottom of ab-l sorber I is an admixture of the solutions originally admitted to said absorber through lines I4 and 3| as previously described. Itpasses from the absorber through line 5, thereafter through the valve of liquid-level regulator 6 to pump 'I which sends it through' line 8 to air-actier 9. The spent solution passes downwardly through the actier 9 in counter-current to a rising flow of air introduced at the bottom thereof byairfan I2, the spent solution being thereby aerated for the liberation of substantially all of the hydrogenl sulphide-which leaves actier 9 admixed'withthe employed air through vent Il.

The major portion of the solution that is now regenerated in respect of hydrogen sulphide, is drawn from the bottom of actifier 8 by pump I3 which sends it through line I4 whereby it is returned to absorber I. Thereafter said solution continues the cycle of absorption and actincation by flowing downwardly in counter-current contact with further quantities of the tobe-puried gas.

A minor portion of the aerated solution in the form of a sidestream, is preferably continuously withdrawn from'tli'e bottom of actiiier 9 by l pump I5 which sends it through line I6 to heat exchanger I1, for preliminary heating by indirect contact with hottersolutions from a subsequent step in the process, the so-heated solution being thereafter flowed through line I8 to this primary absorpt'ibiifsten the bulk of .the y hydrogen sulphide and somecarbon dioxide are removed from the gas whichuthereafter continues to pass upwardly-'through said absorber into counter-current contact with a descending flow of a minor amount of scrubbing solution containing ahigher percentage of the sodium carbonate or a proportionately higher carbonate to bicarbonate ratio than the bulk of -the scrubbing solution introduced through line Il, said minor solution portion being introduced at or near the top of absorber I through line 3|. In this secondary absorption step, the minor solution portion, having a greater'absorptive absorber through line 4.

For actiflcation of the commingled solutions employed in absorber I there: is provided apparaius which may be of the same type of construction as said absorber, however the air- -capacity for hydrogen sulphide, is especially.

the top of pressure actier I9.

Pressure actier I9 can be any type of vaporand-liquid contact apparatus such as one built up of bubble-cap trays or a tower packed with hurdles, spirals, Rasc'hig rings, or the like, and is here shown as a coke-packed tower 20 equipped with a pressure regulator 2| and vent 22 connecting with air-actifier vent Il. Air-fan I2 is preferably driven by a steam turbine 25 with high pressure steam supplied through une u' the exhaust steam from said turbine being-flowed.

. through line 26 and heating coilj located'at'o'r near the bottom of pressure vaefifierl I0 for-purposes of utilizing the heat in exhaust steam from the high pressure steam'gvhioh has employed to drive the air fanfto boil the 1descending solution pressure actifler Is for the removal of carlndioxide from said solution.

The small sidestream ofi'CO: air-regenerated solution introduced -at the top of pressure actiiler I9 through` line I8, as previously described, passes down through said pressure actiiier counter-current to a rising ilow of steam. The volume of said sidestream and the conditions under which it is treated are so chosen that the amount of carbon dioxide here liberated preferably represents that previously absorbed-in one traversing of the absorber.' thereby to continuously maintain its capacity to absorb hydrogen sulphide at the preferred level. The required pressure at which the solution'is boiledfto liberate preferred quantities of carbon -dioxide and incidental quantities of hydrogen sulphide is determined empirically and may vary from atmospheric pressure to three or four atmospheres, said pressure being produced by the heat of indirect turbine exhaust steam in coil 23, which heat generates steam from the solution itself, said generated pressure being maintained at the pre-l the downowing solution in the CO2 pressure;`

. in the bulk of the air-regenerated solution. The

current of steam carrying carbon dioxide and some hydrogen sulphide from the top of pressure actier I9' leaves through pressure-regulator 2l and is expelled through vent lines 22 and Il. With its 'capacity for the further absorption of hydrogen sulphide greatly increased, the pressure regenerated solution is withdrawn from the bottom of actiiier I9 through line 21 to heat ex changer I1 where by indirect contact it gives up its heat to the incoming to-be-treated air-actied solution. thereafter flowing from said heat exchanger through line 28 to solution cooler 29 where it is cooled to the preferred temperature by indirect contact with water and thence returned by pump 30 through line 3| to the top of absorber I where it continues through the cycle of operation by first serving to absorb hydrogen sulphide from the traces thereof in the gas about to leave the absorber.-

The following comparative data derived from a specic application of the present improvement are illustrative of the advantages and results realizable by its employment in the separation and'puriflcation of gaseous mixtures:

A stream of fuel gas that under standard conditions of temperature and pressure showed a content of 1.5 per cent of carbon dioxide and 500 grains of hydrogen sulphide per 100 cubic feety was continuously scrubbed under the said standard conditions of temperature and pressure, at the rate of about60 gallons per M cubic feet, with an aqueous solution having an alkalinity of approximately 30 g. p. l. expressed as sodium carbonate, 0.7 of such sodium present being in the form of NaHCOa and the remainder thereof in the form of NazCOs. The hydrogen-sulphide content of the scrubbed gas that issued from the absorber was 25 grains per 100 cubic feet which represents a removal of 95 per cent of that constituent. Spent scrubbing solution from the absorbent step was continuously aerated countercurrently with a volume of air substantially three times that of the gas being treated and thereafter returned to the absorption step. The process operated satisfactorily for a protracted period and without important change in the stated bicarbonate-carbonate, ratio.

A n alkaline scrubbing solution having the above-given analysiswas similarly employed to treat for the removal of hydrogen sulphide a stream of fuel gas that under standard conditions of temperature and pressure showed the same content of hydrogen sulphide but also contained per cent by volume of carbon dioxide.l

This latter fuel gas was scrubbed at a gauge pressure of 60 pounds per square inch while employing said alkaline solution at a rate of approximately 210 gallons per M cubic feet of the compressed gas. In a short time the sodium bicarbonate content of the scrubbing solution rose from a point where it represented 0.7 of the sodium present in the solution to an amount equaling 0.965 thereof, thus leaving only 0.035 of the sodium present in the form of the carbonate. The removal of hydrogen sulphide rapidly deto absorb the same became so depleted, that a satisfactory removal of hydrogen sulphide could only be obtained by the recirculation of such large quantities of the solution as made its further employment economically prohibitive.

According to the present improvement, spent scrubbing solution from the above-described absorption step for hydrogen sulphide from the fuel gas containing 5 Der cent by volume of carbon dioxide was rst continuously passed through an aeration -stage of actilcation where absorbed hydrogen sulphide was removed and thereafter about per cent of the volume thereof, or at a rate of 52.5 gallons per M cubic feet of gas being treated, was continuously boiled to remove carbon dioxide and the sodium bicarbonate content therein thus reduced to 0.3 of the total sodium combined in the form ofthe carbonate and bicarbonate. 'I'he so-treated solution-fraction was continuously returned to the absorption step along with the air-actiiied solution-portion. The

hydrogen-sulphide content of the purified gas issuing from the absorption step was maintained 'at substantially 5 grains per 100 cubic feet regardless of its initially high carbon-dioxide content. s

It is now possible, simply and economically to effect in a continuous process the removal of hydrogen sulphide from industrial gases also carrying large quantities of carbon dioxide, by 'combining the simplicity of operation of the wellknown Seaboard process for the removal of hydrogen sulphide with an improved and controllable flexibility in the' solution system by the removal of preferred quantities of carbondioxlde from the recycled solution thereby continuously maintaining a high absorption efciency in said recycled solution. The present improved process can -be practiced where the to-be-puried gases are at, above or below atmospheric pressure.

The invention as hereinabove set forth is embodied in particular form and manner but may be lvariously embodied within the scope of the claims hereinafter made.

I claim:

1. In a system for -recovering hydrogen sulphide, the steps of continuously passing a solution of mixed alkali-metal carbonate and bicarbonate into H2S absorption contact with gases containing HzS and such quantities of carbon dioxidethat carbonates of the solution are 'converted to bicarbonates to such an extent that the solution capacity for renewed absorption of HzS is depleted ,after removal of the previously absorbed His; subjecting the entire bulk of solution from the absorption step to a stage of continuous regeneration by countercurrent aeration with air so as to expel substantially only the absorbed HzS; and thereafter, in a second stage vof regeneration, continuously heating under elevated pressure such a minor proportion of the so aerated solution to remove CO2 from bicarbonate therein, and so as to increase the ratio of carbon'- ate to bicarbonate in the minor portion to such an extent above that ratio required in the bulk for renewed absorption of HaS, that the mere ccmmingling of the minor portion with the remainder of aerated solution will restore in the bulk the required ratio of carbonate to bicarbonate for renewed absorption of further HzS from gas as aforesaid; and continuously recommingling the regenerated solutions from both stages in proportion to re-establish the required carbonate to bicarbonate ratio in the entire b'ulk of solution, and renewing the absorption of H28 from gas as aforesaid therewith.

2. In a system for recovering hydrogen sulphide, the steps of continuously passing a solution of mixed sodium carbonate and bicarbonate into H25 absorption contact with gases containing Has and such quantities of carbon dioxide that carbonatos of the solution are .converted to bicarbonates to such an extent that the solution capacity for renewed absorption of HzS is depleted after removal of the previously absorbed HzS; subjecting the entire bulk of solution from the absorption step to a stage of continuous regeneration by countercurrent aeration with air, and

,so as to expel substantially only the absorbed H28; and thereafter, in a second stage of regeneration, continuously heating under elevated pressure such a minor proportion of the so aerated solution to remove CO2 from bicarbonate therein so as to increase the ratio of carbonate to bicarbonate in the minor portion to such an extent above that ratio required in the bulk for renewed absorption of HzS, that the mere commingling of the minor portion with the remainder of aerated solution will restore in the bulk the.

required ratio of carbonate to bicarbonate for renewed absorption of further HzS from gas as aforesaid; and continuously recommingling the regenerated solutions from both stages in proportion to reestablish the required carbonate to bicarbonate ratio in the entire bulk of solution, and renewing the absorption of HzS from gas as aforesaid therewith.

3. In a system for recovering hydrogen sulphide by means of a solution of mixed alkali-metal carbonate and bicarbonate from gases containing such quantities of carbon dioxide as will convert carbonates of the solution to bicarbonates to such an extent that the solution capacity for renewed HzS absorption to the same extent is depleted after removal of the previously absorbed H28, the steps comprising: continuously flowing the entirebulk of the converted solution aforesaid through an aeration actiflcation step and aerating the entire bulk therein by countercurrent flow of air induced by a driven fan to liberate'substantially only the absorbed HzS; continuously-owing a minor portion of the so aerated solution through afurther actiflcation step and boiling itat elevated pressure to remove carbon dioxide from bicarbonate therein; regulating the volume treated as the minor portion and the amount of carbon dioxide driven off therefrom so that the amount of carbon dioxide driven of! from the minor portion represents substantially the amount of carbon dioxide previously absorbed from the gas by the entire bulk of the solution; inducing the flow of air in the aeration actifcation step by flowing high pressure steam through a driving means to operate said air fan, and in amount to maintain the flow of air required in aeration of the total bulk of solution; flowing the eiiiuent steam from the driving means into indirect contact with the solution in said further actifcation step and effecting the boiling of the minor solution-portion and driving off of the carbon dioxide therefrom with .the residual heat of the effluent steam; continuously removing the HzS and CO2 liberated in both actifcation steps from the process after their traversal of the respective actication steps; continuously comminglingsolution from` both actication steps in proportion to re-establish the required carbonate to bicarbonate ratio in the bulk for renewed HzS absorption of gas aforesaid;` and continuously flowing the so commingled solution overl gas as 'aforesaid in the absorption .step of the process for renewed gas purication therein.

'4. In a process comprising a, gaseous absorption step and a spent-solution regeneration step for removing HzS from gas by means of a solution of alkali-metal carbonate-bicarbonate, the steps comprising: in the regeneration step, heating a minor portion only of the bulk of the fouled alkali-metal carbonate-bicarbonate solution, and merely aeratlng the rest of the bulk of the fouled solution by countercurrent flow of aeration air: removing by said aeration the bulk of the hydrogen sulphide absorbed by thebulk of the solution, before returning the solution into contact with the gas in' the absorption step; removing from said minor solution portion, by said heating, a quantity of CO2 which will deplete its bicarbonate content to such an extent below the predetermined level for bicarbonates in the whole solution for HzS absorption, and so regulating the amount of the portion activated as the minor secondary stage.

portion, that the commin-gling of the minor portion with the merely aerated residual majory portion will restore to the bulk the ratio of carbonate to bicarbonate required for renewed absorption of H2S;' vand thereafter commingling the so activated minor portion and the merely aerated portion; and purifying gas aforesaid therewith in the absorption step.

5. In the method of purifying a gas from 'hydrogen sulphide and carbon dioxide which comprises the recirculation-of a regenerable absorbent solution of alkali-metal carbonate and bicarbonate through a cycle comprising an absorption stage in which the solution is brought into contact wit-h the gas, and a regeneration stage in which the solution is regenerated, the improvement which consists in: washing the gas with a flow of absorbent liquid in a primary absorption stage to remove the bulk of its hydrogen sulphide content and with another flow of absorbent liquid in a secondary stage for removal of small traces lof hydrogen sulphide left over in the gas from the primary stage; commingling the liquid from the secondary stage with the aforesaid flow of liquid in the primary stage; regenerating the fouled commingled solution from the primary stage by passing the entire bulkthrough an actiflcation stage in countercurrent relation with a flow of air to remove the bulk of its absorbed HES while leaving the solution depleted in its carbonate content to a level below that required for renewed HzS absorption; recirculating the major portion of the bulk of said depleted solution over the gas in said primary absorption stage; boiling such a proportionate minor portion of the bulk of the so depletedsolution under pressure so as to remove CO2 from bicarbonate to such an extent as to increase its carbonate to bicarbonate ratio to an amount in excessof the ratio required in the bulk 7 of the solution for HzS absorption in the primary absorption stage that the commingling of the bonate required for absorption of the bulk of thev hydrogen `sulphide content of the gas in the primary absorption stage; and recirculating the so boiled minor portieri over the. gas .in said ALFRED R. POWELL. 

